Synthesis of Dendronized Polymers via a “m+n” Grafting-onto Strategy with Reaction-Enhanced Reactivity of Intermediates (RERI) Mechanism

Abstract

Dendronized polymers (DenPols) with tunable shape and surface property have been recognized as a type of promising unimolecular nanomaterials. However, it still has lacked a rapid and efficient approach to the facile synthesis of DenPols with high-generation and well-defined structures. Herein, we report a “ m+n ” grafting-onto strategy combined with the copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction with reaction-enhanced reactivity of intermediates (RERI) mechanism for synthesizing DenPols G _{m+ n} by attaching n-generation dendrons (G n) onto the m-generation DenPols G m. In this “ m+n” grafting-onto strategy, the DenPols G m ( m = 1, 2) bearing 1, 3-triazido branches on the repeating unit were capable of RERI effect that guaranteed the CuAAC reaction in an extremely efficient way with ultrafast kinetics to synthesize third-, fourth- and fifth-generation DenPols (G ₁₊₂, G ₁₊₃, G ₁₊₄, G ₂₊₂, and G ₂₊₃) with near quantitative grafting density and narrow distribution. Moreover, these resultant DenPols G _{m+ n} had more terminal groups per repeating unit due to the three branches of 1, 3-triazido structure, exhibiting valuable potential opportunities for molecular surface engineering. The development of this “ m+ n” grafting-onto strategy with RERI mechanism not only presents a new avenue for ultrafast preparing DenPols but also holds great promise for preparing unimolecular materials with more functional terminal groups.

Keywords

Dendronized polymers / Reaction-enhanced reactivity of intermediates / Grafting-onto strategy / Copper-catalyzed azide-alkyne cycloaddition / Terminal groups / Living polymerization / Functional polymers / Nanostructures

RIGHTS & PERMISSIONS

2025 SIOC, CAS, Shanghai, & WILEY-VCH GmbH.